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United States Patent | 5,322,712 |
Norman ,   et al. | June 21, 1994 |
Chemical Vapor Deposition of copper films is enhanced by simultaneously introducing in the reactor vapor of an organometallic copper precursor and copper complex vapor of a volatile ligand or the hydrate of the ligand.
Inventors: | Norman; John A. T. (Encinitas, CA); Hochberg; Arthur K. (Solana Beach, CA); Roberts; David A. (Carlsbad, CA) |
Assignee: | Air Products and Chemicals, Inc. (Allentown, PA) |
Appl. No.: | 064185 |
Filed: | May 18, 1993 |
Current U.S. Class: | 427/250; 427/124; 427/248.1; 427/255.39; 427/314 |
Intern'l Class: | C23C 016/00 |
Field of Search: | 427/250,255.1,248.1,314,124 |
5085731 | Feb., 1992 | Norman et al. | 156/646. |
5094701 | Mar., 1992 | Norman et al. | 148/23. |
5098516 | Mar., 1992 | Norman et al. | 156/666. |
Jain et al, "Chemical Vapor Deposition of Copper from Hexafluoroacetylacetonato Copper (I) Vinylerimethylsilane", J. Electrochem. Soc. vol. 140, No. 5, Nay 1993 pp. 1434-1439. Donnelly et al, "Copper Metalorganic Chemical Vapor Deposition Reactions of Hexafluoroacetylacetonate Cu(I) Vinylerimethylsilane and Bis(Hexafluoroacetylacetonate) Cu(II) Adsorbed on Titanium Nitride" J. Vac. Sci. Technol. A11(1), Jan./Feb. 1993, pp. 66-77. J. A. T. Norman, et al.; A New Metal-Organic Chemical Vapor Deposition Process of Selective Copper, Metallization Mater. Sci. and Eng. B17(1993) pp. 87-92. F. A. Houle, et. al. Surface Processes Leading to Carbon Contamination of Photochemically Deposited Copper Films, pp. 2452-2458 J. Vac. Sci. Technol. A4(6) Nov./Dec. 1986. C. Oehr, et al; Thin Copper Films by Plasma CVD Copper-Hexafluoro-Acetylacetona App. Phys. A45 1988 pp. 151-154. D. Temple, et al; `Chemical Vapor Deposition of Copper From Copper(II) Hexafluoroacetylacetonate`, J. Electrochem. Soc. 136(11), Nov. 1989 pp. 3525-3529. Rudy L. Van Hemert, et al; Vapor Deposition of Metals by Hydrogen Reduction of Metal Chelates pp. 1123-1126 J. Electrochem. Soc. 112(11) Nov. 1965. D. B. Beach, et al; Low Temperature Chemical Vapor Deposition of High Purity . . . pp. 216-219 Chem. Mater. 1990. W. G. Lai, et al; Atmospheric Pressure Chemical Vapor Deposition of Copper Thin Film J. Electrochem. Soc., vol. 138, No. 11, Nov. 1991, pp. 3499-3504. N. Awaya, et al.; `Deposition Mechanism of Copper CVD`, Conference Proceedings ULSI-VII, MRS 1992, pp. 345-354. P. M. Jeffries, et al; Chemical Vapor Deposition of Copper and Copper Oxidee Thin Films . . . Chemistry of Materials 1989, pp. 8-10. C. R. Moylan, et al; LCVD of Copper: Deposition Rates and Deposit Shapes pp. 1-5; Appl. Phys. A40, 1-5 (1986). C. R. Jones, et al; Photochemical Generation and Deposition of Copper from Jus Phase Precursor, Appl. Phys. Lett. 46(1), Jan. 1985 pp. 97-99. A. E. Kaloyeras, et al; Low-Temperature Metal-Organic Chemical Vapor Deposition . . . J. Electronic Materials, 19(3) 1990 pp. 271-276. T. Ohba, et al; Deposition and Properties of Blanket-W Using Silane Reduction; MRS Ed. by S. Wong et al 1990; pp. 273-279. T. Ohba, et al. Selective Chemical Vapor Deposition of Tungsten Using Silane . . . ; Tech. Dig. IEDM, 213 (1987); pp. 17-24. P. V. Andrews, et al; The Effect of Grain Boundries on the Electrical Resistivity . . . ; Phil. Mag. 19 887 (1969); pp. 887-897. |
TABLE 1 ______________________________________ Specular Reflection Coefficients Wavelength Cu on Au Cu on Pt Cu on Al (nm) Si ref Hfac no Hfac Hfac no Hfac Hfac no Hfac ______________________________________ 440 .429 .447 .366 .344 .286 .366 .366 550 .366 .577 .381 .468 .374 .502 .487 630 .348 .889 .694 .811 .697 .841 .811 ______________________________________